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Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes.

ABSTRACT: Two new mononuclear iron(II) compounds (1) and (2) of the general formula [Fe(L)?](BF?)?·nCH?CN (L = 4-(2-bromoethyn-1-yl)-2,6-bis(pyrazol-1-yl)pyridine, n = 1 for (1) and n = 2 for compound (2)), were synthesized. The room temperature crystallization afforded concomitant formation of two different solvent analogues: compound (1) exhibiting triclinic P-1 and compound (2) monoclinic C2/c symmetry. Single-crystal X-ray studies confirmed the presence of the LS (low-spin) state for both compounds at 180 K and of the HS (high-spin) state for compound (2) at 293 K, in full agreement with the magnetic investigations for both solvent polymorphs. Compound (1) exhibits spin transition above 293 K followed by subsequent solvent liberation, while the spin transition of (2) takes already place at 237 K. After complete solvent removal from the crystal lattice, compound (1d) (the desolvated polymorph derived from (1)) exhibits spin transition centered at 342 K accompanied by a thermal hysteresis loop, while the analogous compound (2d) (the desolvated derivate of compound (2)) remains blocked in the HS state over all the investigated temperature range.

SUBMITTER: Salitros I

PROVIDER: S-EPMC5456902 | biostudies-other | 2016 Jul

REPOSITORIES: biostudies-other

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Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes.

Šalitroš Ivan I Fuhr Olaf O Ruben Mario M

Materials (Basel, Switzerland) 20160719 7

Two new mononuclear iron(II) compounds (1) and (2) of the general formula [Fe(L)₂](BF₄)₂·nCH₃CN (L = 4-(2-bromoethyn-1-yl)-2,6-bis(pyrazol-1-yl)pyridine, n = 1 for (1) and n = 2 for compound (2)), were synthesized. The room temperature crystallization afforded concomitant formation of two different solvent analogues: compound (1) exhibiting triclinic P-1 and compound (2) monoclinic C2/c symmetry. Single-crystal X-ray studies c ...[more]

PMID: 28773709

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Project description:Spin-crossover (SCO) is a reversible transition between low and high spin states by external stimuli such as heat. The SCO behavior and transition temperature (T 1/2) of a series of [FeII(X-pybox)2](ClO4)2 were studied to establish a methodology for ligand-field engineering, where X-pybox stands for 2,6-bis(oxazolin-2-yl)pyridine substituted with X at the 4-position of the pyridine ring. We utilized X = MeO, Me, 3-thienyl, Ph, H, MeS, 2-thienyl, N3, Cl, Br, 3-pyridyl, and 4-pyridyl. The solution susceptometry on five new derivatives with X = Me, 2-thienyl, N3, Br, and 3-pyridyl was performed in acetone, giving the SCO temperatures of 220, 260, 215, 280, and 270 K, respectively. The density-functional-theory molecular orbital (MO) calculation was performed on the ligands with geometry optimization. The atomic charge on the pyridine nitrogen atom [ρ(Npy)] was extracted from the natural orbital population analysis. Positive correlation appeared in the T 1/2 versus ρ(Npy) plot with R 2 = 0.734, being consistent with the analysis using the Hammett substituent constants (σp and σp +). This finding well agrees with the mechanism proposed: the rich electron density lifts the t2g energy level through the dπ-pπ interaction, resulting in a narrow t2g-eg energy gap and favoring the high-spin state and low T 1/2. The MO method was successfully applied to the known SCO-active iron(II) compounds involving 4-substituted 2,6-bis(pyrazol-1-yl)pyridines. A distinct positive correlation appeared in the T 1/2 versus ρ(Npy) plot. The comparison of correlation coefficients indicates that ρ(Npy) is a more reliable parameter than σp or σp + to predict a shift of T 1/2. Furthermore, this method can be more generalized by application to another known SCO family having 3-azinyl-4-p-tolyl-5-phenyl-1,2,4-triazole ligand series, where azinyl stands for a 2-azaaromatic ring. A good linear correlation was found in the T 1/2 versus ρ(NA) plot (NA is the ligating nitrogen atom in the azaaromatic ring). Finally, we will state a reason why the present treatment is competent to predict the SCO equilibrium position only by consideration on the electronic perturbation.

Dataset Information

Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes.

Publications

Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes.

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